Delivery system for agricultural chemicals

ABSTRACT

An emulsifiable concentrate comprising an agriculturally active chemical, a surfactant, an organic diluent and a solvent having first and second components, the first component being capable of solubilizing the agriculturally active chemical and the second component in conjunction with the surfactant being effective to disperse the agriculturally active chemical. The inventive concentrate allows for high concentrations of the active ingredient, exhibits excellent stability and produces highly stable compositions upon dilution with water.

This is a continuation of application Ser. No. 448,707, filed Dec. 11,1989, now U.S. Pat. No. 5,071,463.

BACKGROUND OF THE INVENTION

I. Field of the Invention

The invention relates to a delivery system for agriculturally activechemicals. More particularly, the invention relates to an emulsifiableconcentrate of difficult to dissolve agricultural chemicals.

II. Description of the Prior Art

Agricultural chemicals are most preferably applied in the form ofaqueous emulsions, solutions, or suspensions. Occasionally, they mayalso be applied in the form of a dust wherein the active ingredient isadsorbed onto or mixed with a finely divided inert carrier material,such as, china clay, or the like. With such powdered or dustcompositions, drift due to wind is a problem and consequently, liquidformulations are preferred.

One of the problems with such liquid formulations is the fact thatchemicals having agricultural activity often exhibit extremeinsolubility in water. This results in their having to be dissolvedeither in organic solvents or utilized in the form of emulsions orsuspensions. With respect to the use of organic solvents, these aregenerally disadvantageous from an environmental and cost viewpoint.Particularly, such organic chemicals may exhibit toxicity orside-effects which may be adverse to the effect of the agriculturalchemical itself or to the subsequent fruit or vegetable produced in theparticular agricultural use. This toxicity may also be disadvantageouswith respect to handling.

When attempts are made to provide emulsified or suspension formulations,difficulties are encountered with respect to providing a desirably highconcentration of the agriculturally active ingredient. Thus, when suchagriculturally active chemicals are formulated into an emulsion, it isdifficult to maintain the emulsified state. This makes it difficult tomaintain a uniform formulation, particularly, when the formulation isdiluted with water for application to the plants.

Typically, for example, the agriculturally active ingredient is mixedwith one or more of a variety of conventional solvents and anemulsifying agent to form a concentrate. This concentrate may be anemulsion, suspension, or solution. The concentrate is then stored untilit is transported to the site of use or may simply be transported andstored at the site of use. In any event, the concentrate normally willundergo some period of storage until it is ready for use.Understandably, it is most desirable to be able to transport theagriculturally active ingredient at the highest concentration possibleso as to minimize the volume of material which need be transported. Bythe same token, however, at the use site, it is normally not feasible toadmix ingredients together or to process them other than to dilute theconcentrate with water. Accordingly, it is important that theconcentrate emulsify easily, i.e., exhibit good "bloom", upon theaddition of water. In addition, at the use site, it is often necessaryto store the diluted concentrate for extended time periods until theactual application to the plants. Consequently, it is important that thediluted form of the concentrate exhibit good stability with respect tothe uniformity of the emulsion and to avoid precipitation of the activeingredients. If non-uniformity or precipitation occurs in the dilutedform, then non-uniformity will result in the application of the dilutedformulation to the plants.

An attempt to provide concentrates of agriculturally useful chemicals isdisclosed in South African Patent Application No. 695,393, filed Jul.25, 1969. This application is directed to the formulation of aconcentrate substantially water-insoluble pesticides for agriculturaluse. The pesticides, either in oil or solid form, are mixed withpyrrolidones having a hydrogen or a lower alkyl group containing from 1to 4 carbon atoms attached to the nitrogen atom of the pyrrolidone ring.The application discloses that concentrated solutions of difficult todissolve pesticides could be formulated and that such concentratesexhibited good stability The concentrates utilized are those containingthe pesticidal active ingredient, the particular lower alkylpyrrolidone, a co-solvent which is usually a common organic solvent,such as, an aromatic including xylene, methylated and polyalkylatednaphthalenes and aliphatic solvents, and a dispersing or emulsifyingagent, such as, a surfactant, including polyoxyethylene alkylphenols,polyoxyethylene fatty esters, polyoxyethylene sorbitan fatty esterswhich may be blended with oil-soluble sulfonates, calcium andamino-sulfonate salts, and the like.

This prior art does not offer a solution to the problem arising from thedifficulty in maintaining the stability of the emulsion after theconcentrate is diluted with water. Consequently, unless the diluted formof the concentrate is used immediately after emulsification, it isdifficult to provide a stable diluted formulation for application to theplants.

U.S. Pat. No. 4,798,837 discloses an emulsifiable concentrate of thepesticidal compound (CGA): ##STR1##

This active concentrate contains 10% of the active ingredient using 30%cyclohexanone as the solvent. However, cyclohexanone is highly toxic.For such agricultural uses, it is desirable to avoid the use of toxicsolvents, including those of Lists 1 and 2 of 40 C.F.R. 154.7 dated Apr.22, 1987, which includes inerts of toxicological concern and solventshaving high flash points, as well as to increase the amount of theagriculturally active material in the concentrate.

SUMMARY OF THE INVENTION

We have discovered a novel emulsifiable concentrate of an agriculturallyactive chemical, which concentrate provides, upon dilution, a highlystable emulsion. In addition, the inventive emulsifiable concentratesmay contain relatively high concentrations of the agriculturally activeingredient making it advantageous from both economic and handlingviewpoints. Also, the concentrates of the present invention utilizeorganic materials which do not pose environmental problems either in useor handling.

More particularly, the emulsifiable concentrate of the present inventionis composed of an agriculturally active chemical, a surfactant, anorganic diluent, and a solvent having a first component and a secondcomponent.

The first component of the solvent is selected from those compoundswhich have a sufficiently high hydrophilic property to solubilize theagriculturally active chemical. Preferably, the first component willhave the following Hansens' solvent parameters:

Dispersable component from about 40 to 50%;

Polar components of from about 25 to 40%; and

H-bonding components of 10 to 30%.

The second component is a hydrophobic solvent having the followingHansens' solubility parameters:

Dispersive component from about 56 to 75%;

Polar component from about 8 to 24%; and

H-bonding component of from about 10 to 30%.

This second component should also have surfactant properties and act asa non-ionic surfactant with an HLB value ranging from about 2 to 8.

For a discussion of the solubility parameters, see C.R.C. Handbook ofSolubility Parameters and Other Cohesion Parameters, Allan F. M. Barton,1983, Table 9, p. 167-170.

DESCRIPTION OF THE PREFERRED EMBODIMENT

As used herein, the term "agriculturally active chemical" includescompounds and mixtures thereof which can be used as agriculturalfertilizers, nutrients, plant growth accelerants, herbicides, plantgrowth controlling chemicals, and chemicals which are effective inkilling plants, insects, microorganisms, fungi, bacteria and the likewhich are commonly referred to as insecticides, bactericides,fungicides, nematocides, fumigants, and the like, as well as any otherchemicals having properties which are suitable for agricultural uses interms of application to plants or domestic uses for controlling insectsand pests. Particularly, such chemicals would normally take the form ofwater-immiscible or oily liquids and/or solids which is substantiallyinsoluble in water. By the term "substantially insoluble", it is meantthat for all practical purposes, the solubility of the compound in wateris insufficient to make the compound practicably usable in anagricultural end use without some modification either to increase itssolubility or dispersability in water, so as to increase the compound'sbioavailability or avoid the use of excessively large volumes ofsolvent.

Suitable agriculturally active chemicals which can be used with thepresent invention include insecticides, such as, cyclocompounds,carbamates, animal and plant derivatives, synthetic pyrethroids,diphenyl compounds, non-phosphates, organic phosphates, thiophosphates,and dithiophosphates. (See Agricultural Chemicals, Book I, Insecticides,1989 Revision by W. T. Thomson, Thomson Publications.) Typical of theinsecticides are:

    ______________________________________                                        cyclocompounds:                                                                            6,7,8,9,10,10-hexachloro-                                                     1,5,5a,6,9,9a-hexahydro-6,9-methano-                                          2,4,3-benzodioxathiepin-3-oxide                                  carbamates:  2-isopropyl phenyl-N-methyl                                                   carbamate;                                                                    2-(1,3-dioxolan-2yl) phenylmethyl                                             carbamate;                                                                    2,3-isopropylidine dioxyphenyl                                                methyl carbamate;                                                animal and plant                                                                           chlorinated hydrocarbons derived                                 derivatives: from Southern pine; naturally                                                 occuring lactone glycoside;                                      synthetic    (±) α-cyano-3-phenoxybenzyl (±) cis,                 pyrethroids: trans 3-(2,2-dichlorovinyl)-2,2-di-                                           methyl cyclopropane carboxylate;                                              (±) cyano (3-phenoxyphenyl methyl                                          (±)-4-(difluoromethyoxy) α-(-1-                                      methylethyl) benzene acetate;                                    phenoxy compounds                                                                          2,2-bis(p-methoxy phenyl)-1,1,1,tri-                             and non-phosphate:                                                                         chloroethane;                                                                 1,3,5,tri-n-propyl-1,3,5-triazine-                                            2,4,6 (1H,3H,5H) trione;                                                      ethyl (2E, 4E)-3,7,11-trimethyl-2,4-                                          dodeca dienoate;                                                              1-decycloxy 4-[(7-oxa-oct-4-ynyl)]-                                           oxybenzene;                                                      organic phosphates:                                                                        dimethyl phophate ester of 3-hy-                                              droxy-N,N-dimethyl-cis-crotonamide;                                           2-chloro-1-(2,4-dichloro phenyl)                                              vinyl diethylphosphate;                                                       4-(methyl thio) phenyl dipropyl                                               phosphate;                                                       thiophosphates:                                                                            0,0-diethyl-0-4-nitrophenyl phos-                                             phorothioate;                                                                 0,0-diethyl-0-(2,isopropyl-6-methyl-                                          5-pyrimidinyl) phosphorothioate;                                              2-diethylamino-6-methyl pyrimidine-                                           4-yl dimethyl phosphorothioate;                                  dithiophosphates:                                                                          0,0-dimethyl phosphorodithioate                                               ester of diethylmercapto succinate                                            0-ethyl-S-phenyl ethyl phosphorodi-                                           thioate.                                                         ______________________________________                                    

Typical herbicides include phenoxy compounds, benzoic, acetic, andphthalic acids, aniline derivatives, nitriles, amides acetamides,anilides, carbamates, thiocarbamates, and heterocyclic nitrogenderivatives, e.g., triazines, pyridines, pyridazones, picolinic acid,and urea derivatives and phosphates. (See Agricultural Chemicals, BookII, Herbicides, 1986-87 Edition, W. T. Thomson, Thomson Publications,Fresno, Calif. 93791.) Exemplary of the above compounds are:

    ______________________________________                                        phenoxy compounds:                                                                         2,4-Dichlorophenoxy acetic acid                                               2,4,5-trichloro phenoxyacetic acid;                                           4-(2,4-dichlorophenoxy) butyric                                               acid;                                                                         S-ethyl 2 methyl-4-chlorophenoxy-                                             thioacetate;                                                                  2-methyl-4-chloro-phenoxy acetic                                              acid;                                                                         methyl 5-(2,4-dichloro-phenoxy)-2-                                            nitrobenzoate;                                                   benzoic and acetic                                                                         3,6-dichloro-o-anisic acid                                       acids of phthalic                                                                          4-chloro-2-oxo benzothiazolin-3-yl                               compounds:   acetic acid;                                                                  N-1-Naphthyl-phthalamic acid;                                    nitriles and aniline                                                                       3-5-dibromo-4-hydroxybenzo-nitrile;                              derivatives: α,α,α,trifluoro-2,6-dinitro-N,                              N-dipropyl-p-tolinidine;                                                      N-(1-ethylpropyl)-2,6-dinitro-3,4-                                            xylidine;                                                        amides, acetamides,                                                                        N,N-diethyl-2-(1-naphthalenyl oxy)-                              anilides:    propionamide;                                                                 2,6-dimethyl-N-2' methoxy-ethyl-                                              chloro-acetanilide;                                                           3',4'-dichloro-propionanilide;                                                α-chloracetic-N-(3,5,5-trimethyl-                                       cyclohexen-1-yl)-N-isopropylamide;                                            4-benzyl-N-isopropyl trimethyl                                                acetamide;                                                       thiocarbamates:                                                                            S-Ethyl dipropyl thiocarbamate;                                  urea derivatives:                                                                          3-(5-tert-butyl-3-isoxazoyl)-1,1-                                             dimethyl urea;                                                                N-(2,6-trifluoro-benzoyl)-N'-[2,5-                                            dichloro-4-(1,1,2,3,3,3-hexafluoro-                                           propyloxy) phenyl] urea;                                         pyrrolidone  1-(m-trifluoro methyl phenyl)-3-                                 derivatives: chloro-4-chloromethyl-2-pyrrolidone;                             amino acid   methyl N-benzoyl-N-(3-chloro-4-                                  derivatives: fluorophenyl)-DL alarinate;                                                   N-chloroacetyl-N-(2,6-diethyl                                                 phenyl)-glycine ethyl ester;                                     carbamates:  Isopropyl-m-chlorocarbanilate;                                                3-Ethoxy (carbonyl aminophenyl)-N-                                            phenyl carbamate;                                                heterocyclics:                                                                             4-amino-3,5-dichloro-6-fluoro-2-                                              pyridyloxy acetic acid;                                                       4-(1,2-Dimethyl-N-propyl amino)-2-                                            ethyl amino-6-methyl thio-S-                                                  triazine;                                                                     2-[4,5-dihydro 4-methyl-4-(1-methyl                                           ethyl)-5-oxo-1 H-imidazoyl-2yl-3-                                             byridinecarboxylic acid;                                                      2-[3,5-dichlorophenyl)-2-(2,2,2-                                              trichloroethyl) oxinane;                                                      Butyl-9-hydro-fluorene-(9)-                                                   carboxylate;                                                                  2-[1-(ethoxy imino) butyl]-3-                                                 hydroxy-5-(2H-tetra hydro thiopyran-                                          3-yl)-2-cyclohexene-ione;                                                     2-(2 chlorophenyl) methyl-4,4-                                                dimethyl-3-iso oxazolidinone;                                    phosphates:  0-ethyl-0-(3-methyl-6-nitro phenyl)                                           N-sec-butyl phosphoro thio amidate.                              ______________________________________                                    

Typical fungicides include (See Agricultural Chemicals, Book IV,Fungicides, 1989 Revision, W. T. Thomson, Thomson Publications, Fresno,Calif. 93791):

    ______________________________________                                        organic compounds:                                                                         2,5-dimethyl-N-Cyclohexyl-N-methoxy-                                          3-furan carboxamide;                                                          5-Ethyoxy-3-trichloromethyl-1,2,4-                                            thiadiazole;                                                                  3-(2-methyl piperidino) propyl 3,4-                                           dichlorobenzoate;                                                             N,N'-(1,4-piperazinediyl bis (2,2,2-                                          trichloro) ethylidene) bis                                                    formamide;                                                                    Tetramethyl thiuram disulfide:                                                0-Ethyl-S,S,diphenyl-dithiophos-                                              phate;                                                                        5,10-dihydro-5,10-dioxo naphtho                                               (2,3,9)-p-dithiin-2,3-dicarbo-                                                nitrile;                                                                      2-(Thiocyano methyl thio) benzothia-                                          zole;                                                                         α-2-(4-chlorophenyl) ethyl]-α-(1,1-                               dimethyl ethyl)-1 H-1,2,4-triazole-                                           1-ethanol;                                                       morpholines: N-tridecyl-2,6-dimethyl morpholine;                                           4-N-dodecyl-2,6-dimethyl morpholine;                             ______________________________________                                    

Typical fumigants, growth regulators, repellants, and rodenticidesinclude (See Agricultural Chemicals, Book III, Fumigants, 1988-1989Revision, W. T. Thomson, Thomson Publications, Fresno, Calif. 93791):

    ______________________________________                                        growth regulants:                                                                           1,2 Dihydro-6-ethyoxy-2,2,4-tri-                                              methylquinoline;                                                              (2-chloroethyl) phosphoric acid;                                              4-[acetamino) methyl]-2-chloro-N                                              (2,6-diethyl phenyl acetamide;                                                Benzoic acid, 3,6 dichloro-2-                                                 methoxy,2-ethoxy-1-methyl-2-oxo                                               ethyl ester;                                                    repellants:   0,0-dimethyl-0-[(4-methyl thio)-m-                                            tolyl] phosphorothioate;                                                      Tetriary butyl-sulfenyl dimethyl                                              dithio carbamate;                                               seed softener:                                                                              2-chloro-6-(trichlomethyl) pyridine;                                          5-ethoxy-3-trichloromethyl-1,2,4-                                             thiadiazole;                                                                  N-phenyl-N'-1,2,3-thiadiazol-5-yl                                             urea;                                                           ______________________________________                                    

Pesticides may be characterized by their physical properties, dependingon their physical state at normal or ambient conditions, i.e., between40° F. and 90° F. and their solubility or miscibility with water orother common organic solvents, e.g., aromatics, such as, toluene,xylene, methylated and polyalkylated naphthalenes, and aliphaticsolvents.

Based on the physical properties, the pesticides may be classified intotwo groups. The first group includes those which are oily liquids atambient temperatures and are immiscible with water. Specific pesticidesinclude:

Common esters of 2,4-dichlorophenoxyacetic acid,

Common esters of 2,4,5-trichlorophenoxyacetic acid,

Common esters of 2-(2,4-dichlorophenoxy) propionic acid,

Common esters of 2-(2,4,5-trichlorophenozy) propionic acid,

Common esters of 2,4-dichlorobutyric acid,

Common esters of 2,methoxy-3,6-dichlorobenzoic acid,

Common esters of 2-methyl-4-chlorophenoxyacetic acid,

Piperonyl butoxide 3,4-methylenedioxy-6-propyl benzyl n-butyl diethyleneglycol ether,

Bromophos ethyl: 0,0-diethyl-0-2,5-dichloro-4-bromophenylthionophosphate,

N-(2-mercaptoethyl) benzene-sulfenamide (BETASAN®),

Isobornyl Thiocyanoacetate (Thanite®),

Ioxynil ester of octanoic acid,

Molinate S-ethyl hexahydro - 1 H - azepine-1-carbothioate,

PP 511 0,0-dimethyl-(2-diethylamine 4-methyl-6-pyrimidinyl) carbamate,

PP 211 0,0-diethyl 0-(2-diethylamine-4-methyl-6-pyrimidinyl)phosphorocarbamate, Chlordane

5-Ethoxy-3-(trichlorometyl)-1,2,4-thiadiazole (TERRAZALE®),

Ethyl-s-s-dipropyl-phosphodithioate (MOCAP®),

S-Ethyl dipropylthiocarbamate (EPTAM®),

S-Ethyl diisobutylthiocarbamate (SUTAN®),

S-n. propyl-di-n-propylthiocarbamate (VERNAM®),

S-propyl butylethylthiocarbamatae (TILLAM®),

S-ethyl ethylcyclohexylthiocarbamate (RO-NEET®),

Malathion (S-(1,2-dicarboxyethyl)-0,0-dimethyl phosphorodithioate),

Diazinon (0,0-diethyl,0-(2-isopropyl-4-methyl-6-pyrimidinyl)phosphorothioate,

O-Ethyl-S-phenyl-ethylphosphonodithioate (DYFONATE®), Toxaphene(Octachlorocamphene),

Bromoxynil (3,5-dibromo-4-hydroxy benzonitrile ester of n.octanoic acid,

2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide (LASSO®),

Diallate S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate, TriallateS-2,33-trichloroallyl N,N-diisopropylthiolcarbamate.

The second group comprises those pesticides which are solids at ambienttemperatures and for all practical purposes, insoluble in water.

2,4,5-T (2,4,5-trichlorophenoxy acetic acid)

Monuron (3-(p-chlorophenyl)-1,1-dimethyl urea)

Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl urea)

Bromacil (5 bromo-3-sec. butyl-6-methyl uracil)

Isocil (5 bromo-3-isopropyl-6-methyl uracil)

Linuron (3-(3,4 dichlorophenyl)-1-methoxy-1 methyl urea

Atrazine (2-chloro-4-ethylamino-6 isopropylamino-s-trriazine)

Simazine (2-chloro-4,6,-bis (ethylamino)-s-triazine

Dodine (n-dodecylguanidine acetate)

Thiram (tetramethylthiuram disulfide)

N-(mercaptomethyl)phthalimide s-(o,o dimethylphosphorodithioate)(IMIDAN®)

Lindane (gamma 1,2,3,4,5,6 hexachlorocyclohexane)

Folpet (N-trichloromethylphthalimide)

Manazon (s-(4,6-diamino-1,3,5-triazin-2-yl methyl)dimethylphosphorothiolthionate)

Barban (4-chloro-2 butynyl m-chlorocarbanilate)

Tricumba 2-methoxy-3,5,6-trichlorobenzoic acid

Trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylamiline) (2,3dihydro-5-carboxanilido-6-methyl-1,4-oxathiin) (VITAVAX®)

2,4-dichlorophenoxyacetic acid

4-(4-chloro-2 methylphenoxy) butyric acid

2-(2,4-dichlorophenoxy) propionic acid

Ioxynil: 3,5 diiodo-4-hydroxybenzonitrile

Bromoxynil: 3,5 dibromo-4-hydroxybenzonitrile

Carbaryl: 1-naphthyl-N-methylcarbamate

Methoxychlor: 2,2,-Bis(p-methoxyphenyl)-1,1-trichloroethane

PP 781: 4(2-chloro phenylhydrazono)-3-methyl-5-isoxazolone*

PP 675: 5-butyl-2-dimethylamino-4-hydroxy-6-methyl pyrimidine*

PP 062: 5,6-dimethyl-2-dimethylamino-4 pyrimidinyl dimethylcarbamate*

PP 149: 5-n-butyl-2 ethylamino-4-hydroxy-6 methylpyrimidine*

C 6313 N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea

C 6989 2,4'dinitro-4-trifluoromethyl-diphenylether

Chloroxuron N'-4-(chlorophenoxy) phenyl-NN-dimethylurea

Dichlobenil 2,6-dichlorobenzonitrile

Diphenamid NN-dimethyl-2,2-diphenylacetamide

Fenac 2,3,6-trichlorophenylacetic acid

Fluometuron N'-(3-trifluoromethylphenyl)-NN-dimethylurea

GS 14260 4-ethylamino-2-methylthio-6-t-butyl-amino-1,3,5-triazine

PCP Pentachlorophenol

Lenacil3-cyclohexyl-6,7-dihydro-1H-cyclo-pentapyrimidine-2,4-(3H,5H)-dione

Pyrazon 5-amino-4-chloro-2-phenyl-3-pyridazone

Metrobromuron N'-(4-bromophenyl)-N-methoxy-N-methylurea

MetoxymarcN-(4-methoxybenzoyl)-N-(3,4-dichlorophenyl)-N',N'-dimethylurea

Neburon N-butyl-N'-(3,4-dichlorophenyl-N-methylurea

NIA 11092 1,1-dimethyl-3-[3-(n-t-butyl carbamyloxy)phenyl] urea

Mecoprop 2-(4-chloro-2 methylphenoxy)propionic acid

Monolinuron N'-(4-chlorophenyl)-N-methoxy-N-methylurea

Nitrofen 2,4-dichlorphenyl 4-nitrophenylether

Propanil N-(3,4-dichlororphenyl)propionamide

Pyriclor 2,3,5-trichloro-4-pyridinol

Solan 3'-chloro-2-methyl-p-volerotoluidide

Terbacil 5-chloro-3-t-butyl-6-methyluracil

UC 22463 (SIRMATE)-3,4-dichlorobenzyl N-methylcarbamate

WL 9385 2-Azido-4-ethylamino-6-t-butylamino-s-triazine

Propachlor 2-chloro-N-isopropylacetanilide

CP 50144 2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide

CP 31675 2-chloro-N-(2 methyl-6-t-butylphenyl)acetamide

Cypromid 3',4'-dichlorocyclopropane carboxanilide

Fenuron NN-dimethyl-N'phenylurea

Chlorbromuron N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea

Ametryne 2-methylmercapto-4-ethylamino-6-isopropyl-amino-s-triazine

Prometryne 2-methylmercapto-4,6-bisisopropyl amino-s-triazine

DCPA dimethyl 2,3,5,6, tetrachloroterephthalate

Benefin N-butyl-N-ethyl-2,2,2-trifluoro-2,6-dinitro-p-toluidine

Nitralin 2,6-dinitro-4-methylsulfonyl-NN-dipropyl-aniline

PP 493 2,6-difluoro-3,5-dichloro-4-hydroxy pyridine

CNP 2,4,6-trichlorophenyl-4'-nitrophenyl ether

Pentachloro nitrobenzine

1-(butile carbamoyl)-2-benzimidazol carbamic acid, methyl ester(BENLATE®)

Typical examples of first components suitable for use in the solvent arealkylpyrrolidones having from 1 to 4 carbon atoms in the alkyl group,cyclic lactones, e.g., gamma-butyrolactone, lower alkyl cycliccarbonates, i.e., ethylene carbonate, propylene carbonate, butylenecarbonate, lower akylimidazolone, e.g., N-N,dimethylimidazolone, loweralkylamides of formic acid and acetic acid, e.g., dimethyl formamide anddimethylacetamide, and lower alkyl sulfoxides, e.g., dimethylsulfoxide.(The term "lower alkyl" in these examples means one or two carbons.)Mixtures of these may also be used as the first component.

Examples of appropriate second components include alkylpyrrolidoneshaving an alkyl portion containing from 6 to 14 carbon atoms, e.g.,octylpyrrolodone, dodecylpyrrolidone, or N-(2'-ethylhexylpyrrolidone),alkyl gamma-butyrolactones, alkyl cyclic carbonates and combinationsthereof, wherein the alkyl chains contain from 6 to 14 carbon atoms. Thealkyl portion may be distributed at one or more sites on the ring solong as one portion contains at least 6 carbon atoms and the totalnumber of alkyl carbon atoms does not exceed 14. For each of the aboveexamples, the 6 to 14 carbon alkyl portions may be straight or branched.

Preferably, the first component is selected from the group consisting ofpyrrolidones having the formula ##STR2## wherein R is hydrogen or loweralkyl having from 1 to 4 carbon atoms and R₁ is lower alkyl having from1 to 4 carbon atoms.

The second component is preferably selected from pyrrolidones having theformula ##STR3## wherein R₂ is hydrogen or alkyl having from 6 to 14carbon atoms and R₃ is alkyl having from 6 to 14 carbon atoms with theproviso that at least one of R₂ or R₃ must contain at least 6 carbonatoms and the sum of the carbon atoms in R₂ and R₃ cannot exceed 14.

The inventive composition further comprises an organic diluent which isa synthetic or naturally occurring oils having a high hydrophobiccharacter or having a fractional dispersive solubility parameter ofgreater than 70% and preferably greater than 85% and a molar volume ofgreater than 90 cm³ /mole. These properties are defined in the C.R.C.Handbook referred to hereinabove. Typical diluents include soybean oil,rapeseed oil, long chain alcohols, long chain ketones, long chainesters, and ethers. As used herein, "long chain" means with 6 or morecarbon atoms. Also suitable as the organic diluent are aromaticpetroleum oils including those which are commercially availabledistillates from crude oils having an average boiling point greater than200° C. Typical of such materials are those sold under the trademarksExxon 200 or Texaco 400. Of course, such aromatics should be approvedfor use as a carrier for agriculturally active chemicals.

The composition of the aromatic petroleum oil is generally:

Heavy aromatic solvent naphtha--about 60%;

Middle distillate solvent extractant--about 40%.

Normally, these oils contain predominantly the C₉ -C₁₅ aromatichydrocarbons and primarily the C₁₀ -C₁₂ hydrocarbons having a flashpoint of about 203° F.

In the inventive composition, the amount of solvent is in the range fromabout 20 to 90%, and the amount of diluent is about 80 to 10%, based onthe weight of solvent and diluent in the composition. With respect tothe so)Vent, the amount of the first component is from about 5 to 95%,and preferably, 20 to 80%; and the amount of the second component isfrom about 5 to 95%, and preferably, 20 to 80%, based on the weight ofthe solvent.

The inventive composition also contains one or more additionalemulsifier or surfactant which is generally selected on a case by casebasis in order to optimize the solubility and stability of the emulsion.Typically, such emulsifiers include ethoxylated alkyl phenols, linearaliphatic polyesters, linear aromatic polyesters, polyethoxylatedalcohols, linear aliphatic ethoxylates, polyethoxylated castor oil,polyethoxylated carboxylates, and polyethoxylated alkylamines. Anionicsurfactants may be used as the emulsifier and include phosphate estersand their salts, alkyl sulfonamides, salts of sulfatednonylphenoxypoly(ethyleneoxy) ethanol, salts of alkylbenzene sulfonates,salts of alkylnaphthalene sulfonate, and sulfonated aliphatic polyestersand their salts. Also suitable are complex phosphate esters of nonionicsurfactants of the ethylene oxide type which are mixtures of diesters ofphosphoric acid. (See, for example, McCutcheon's, Emulsifiers andDetergents (1989), published by McCutcheon's Division of M.C. PublishingCo., Glen Rock, N.J.) Generally, the amount of emulsifier (surfactant)is from about 1 to 25% based on the total weight of the composition.

The agriculturally active chemical (sometimes referred to herein as AAC)concentration should be as high as possible so long as it does notprecipitate out upon dilution of the concentrate with water for areasonable period of time and achieves the desired effect. With thepresent invention, it is possible to obtain concentrates withagriculturally active chemical concentrations in excess of 5 weightpercent which form a stable emulsion upon being diluted with water.Depending on the particular agriculturally active chemical, theconcentration of the AAC is from about 5 to 60% based on the totalweight of the composition before dilution.

The following examples illustrate the present invention*:

EXAMPLE 1

A series of twelve compositions wherein the amount of a firstpyrrolidone component (N-methylpyrrolidone), second pyrrolidonecomponent (N-octylpyrrolidone) and aromatic solvent were varied using asurface-active agent from 14.3% to 22.2% by weight and agriculturallyactive chemical from 25.8% to 41.6% by weight. (See Table 1.) Thesurface-active agent was Gafac RE-610 (ethoxylated phosphate ester), andthe agriculturally active chemical (AAC) wasN-(1-ethylpropy)-2,6-dinitro-3,4-xylidine (PRL).

FORMULATIONS

Formulations were made by mixing together the components comprising ofeach composition by weighing the exact proportion of ingredients in abottle. The solvents were weighed in first. The AAC was dissolvedcompletely in the solvent system followed by addition of the wettingagent or emulsifying agent. Typically, about 20 g of each of theformulations was prepared. As an illustration, formulation #11 includedin Table 1-2 was prepared by weighing together the following ingredientsin a one ounce bottle:

                  TABLE 1-1                                                       ______________________________________                                        N-methylpyrrolidone 2.75 g  20.4%                                             N-octylpyrrolidone  1.25 g  9.3%                                              Aromatic Petroleum oil -                                                                          1.00 g  7.4%                                              Exxon 200                                                                     PRL                 5.50 g  40.7%                                             (N-1 ethyl propyl)-2,6-                                                       dinitro-3,4-xylidine                                                          (92% Tech.)                                                                   Phosphate ester     3.00 g  22.2%                                             (Gafac RE-610)                                                                TOTAL:              13.50 g 100.0%                                            ______________________________________                                    

The contents were stirred well in an automatic rocking shaker for about30 minutes when the AAC dissolved completely. The samples thus preparedwere evaluated for freeze-thaw stability on storage and ease ofemulsification and emulsion stability on dilution.

FREEZE-THAW STABILITY

The concentrates were stored for a period of 24 hours in the cold(temperature 5° C.) in a refrigerator and taken out and thawed to roomtemperature and then stored at 55° C. in an oven for a period of 24hours. The alternate storage in the cold (5° C.) and warm condition at55° C. was repeated for three cycles. Any separation during the storagewas recorded. A concentrate is "stable" if there is no substantialseparation after the 24 hour cycles at each temperature.

Evaluation of Emulsion Stability and Ease of Emulsification

A Nessler tube (1.8 cm diameter; 28 cm long) was filled with appropriatequantity (47-48 g) of World Health Organization (WHO) standard (6 g ofCaCl₂ and 2.78 g of MgCl₂ 6H₂ O dissolved in 20L) hard water having ahardness of 342 ppm expressed as Na equivalent. Using a serologicalpipette, 0.5-2.5 g of emulsion concentrate was dropped into the Nesslertube containing 47.5-49.5 g water. The initial bloom was observed atzero time without stirring and the quality of the bloom was graded byvisual appearance as shown below. The Nessler tube was stopped andinverted 20 times; the bloom was again recorded and so also stability asjudged by volume or height of the sedimentation (cream/ppt/oil) followedat different intervals of time: 0, 1 hour, 2 hours, up to 24 hours.

Stability of Diluted Concentrate

The composition of the cencentrate (EC) diluted with water wasconsidered "stable" if at EC concentrations of from 0.2 to 1%, thecomposition after mixing (twenty inversions) exhibited two mm or lesscream and no oil in one hour. Both top and bottom should be checked.

    ______________________________________                                        Bloom:  Excellent Thick emulsion cloud with no                                                  separation                                                          Good      Emulsion cloud may be thin, or may                                            exhibit trailing, small number of oil                                         droplets within cloud                                               Poor      Many oil droplets within cloud, some                                          droplets separate from cloud                                ______________________________________                                    

Each of the emulsifiable concentrates thus prepared were analyzed forease of emulsification (bloom) upon addition of water and after twentyinversion of the sample as well as emulsion stability upon dilution withwater. The composition of the samples are set forth in Table 1-2 and theresults of the analysis are set forth in Table 1-3. The freeze-thawstability was measured as follows: Compositions 1 through 7 included inTable 1-2 passed freeze-thaw stability test when stored at -10° C. to55° C. for 3 cycles of 24 hour periods. Compositions 8 through 12included in Table 1-2 passed freeze-thaw stability test when stored at5° C. to 55° C. for 3 cycles of 24 hour periods. Formulations 11 showedmaximum freeze-thaw stability with PRL at 40.7%.

                                      TABLE 1-2                                   __________________________________________________________________________    Ingredient  1   2   3   4    5   6   7   8    9   10  11  12                  __________________________________________________________________________    N-methylpyrrolidone                                                                       30.0                                                                              33.0                                                                              0   30.0 24.0                                                                              60.0                                                                              0   18.2 22.2                                                                              29.7                                                                              20.4                                                                              14.8                (M-Pyrol)                                                                     N-octylpyrrolidone                                                                        30.0                                                                              15.0                                                                              0   0    18.0                                                                              0   60.0                                                                              7.3  6.7 3.7 9.3 11.0                (LP-100)                                                                      Aromatic oil                                                                              0   12.0                                                                              60.0                                                                              30.0 18.0                                                                              0   0   11.0 8.2 3.7 7.4 11.0                (Exxon 200)                                                                   Gafac RE-610                                                                              14.3                                                                              14.3                                                                              14.3                                                                              14.3 14.3                                                                              14.3                                                                              14.3                                                                              21.9 22.2                                                                              22.2                                                                              22.0                                                                              22.0                PRL, 92% Tech.                                                                            25.9                                                                              25.9                                                                              25.8                                                                              25.8 25.8                                                                              25.8                                                                              25.8                                                                              41.6 40.7                                                                              40.7                                                                              40.7                                                                              41.2                Solvent ratio                                                                 M-pyrol     50  55  0   50   40  100 0   50   60  80  55  40                  LP-100      50  25  0   0    30  0   100 20   18  10  25  30                  Ar. Exxon 200                                                                             0   20  100 50   30  0   0   30   22  10  20  30                  Water used for                                                                            WHO WHO WHO WHO  WHO WHO WHO WHO  WHO WHO WHO WHO                 dilution                                                                      hardness ppm                                                                              342 342 342 342  342 342 342 342  342 342 342 342                 Concentration                                                                             0.65                                                                              0.65                                                                              0.65                                                                              0.65 0.65                                                                              0.65                                                                              0.65                                                                              0.83 0.83                                                                              0.83                                                                              0.83                                                                              0.83                of AAC (% in                                                                  diluted sample)                                                               __________________________________________________________________________

                                      TABLE 1-3                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                                 Stability                                                                     Thickness of                                                   Bloom          Separation                                                                           Separation after                                        Bloom at After 20                                                                            cream, oil or                                                                        Mixing and standing for:                                Zero Time                                                                              Inversions                                                                          precipitation                                                                        1    2    24                                            *        **    at 0 time                                                                            hours                                                   __________________________________________________________________________    1  poor-fair                                                                           excellent                                                                            20 mm <1 mm                                                                              <1 mm                                                                              crystals                                                     cream ppt        to the top                                    2  excellent                                                                           excellent                                                                           0      0    0    0                                                spont.                                                                     3  excellent                                                                           excellent                                                                            2 mm   2 mm                                                                               2 mm                                                                                2.5 mm                                      4  excellent                                                                           excellent                                                                           <1 mm  <1 mm                                                                               1 mm                                                                               1 mm                                         5  excellent                                                                           excellent                                                                           0      0    0    0                                                spont.                                                                     6  excellent                                                                           excellent                                                                           0      0    0    <1 mm                                         7  poor  excellent                                                                            1 mm  <1 mm                                                                               1 mm                                                                               4 mm                                                                         cream on                                                                      bottom                                                                         4 mm                                                                         oil on top                                    8  excellent                                                                           excellent                                                                           <1 mm  trace                                                                              trace                                                                              trace                                         9  excellent                                                                           excellent                                                                           0      0    0    trace                                         10 excellent                                                                           excellent                                                                           trace  0    0    <1 mm                                            spont.                                                                     11 excellent                                                                           excellent                                                                           trace  0    0    trace                                            spont.                                                                     12 excellent                                                                           excellent                                                                           <1 mm  trace                                                                              trace                                                                              trace                                            spont.                                                                     __________________________________________________________________________     *The descriptions have the following meanings:                                poor-fair  emulsion produced between one and five minutes                     excellent  emulsion produced after two seconds                                spontaneous  emulsion produced instantly                                      **excellent  complete emulsification obtained. Thick emulsion cloud with      no separation.                                                                **good  emulsion cloud may be thin, or may exhibit trailing, small number     of oil droplets within cloud                                                  **poor  many oil droplets within cloud, some droplets separate from cloud

EXAMPLE 2

A second series of two experiments was carried out using the followingformulation:

                  TABLE 2-1                                                       ______________________________________                                        1.         CGA (98% Tech.)   22.2%                                            2.         N-methylpyrrolidone                                                                             33.3%                                            3.         N-octylpyrrolidone                                                                              16.7%                                            4.         Texaco Aromatic 400                                                                             16.7%                                            5.         Gafac RE-610 (GAF)                                                                              11.1%                                                                         100.0%                                           ______________________________________                                    

This composition was prepared by weighing out the individual quantitiesof the ingredients and adding the anionic emulsifier (5) to theN-methylpyrrolidone, admixing the agriculturally active chemical to thismixture, adding the N-octylpyrrolidone to the resulting mixture, andfinally, adding the aromatic diluent (4) and mixing the entirecomposition to make it uniform. The formulation thus prepared was clear.Samples of the formulation were stored at -10° C. and 55° C. for each ofthree 24 hr. periods. No precipitation nor separation of any of theingredients was observed for the samples.

The concentrate thus prepared was diluted in a standard 37 cm×2 cmNessler's tube using WHO standard water. Two dilutions of emulsifiableconcentrate to water of 5:100 and 0.6:100 were prepared. The bloomcharacteristics and emulsion stabilities of each of these dilutions areset forth in Table 3.

                  TABLE 2-2                                                       ______________________________________                                        EMULSION STABILITY AND                                                        BLOOM CHARACTERISTICS                                                                      Formulation                                                                   I.         II.                                                   ______________________________________                                        Conc. of active                                                                              22%          22%                                               Dilution:      2.5:47.5     0.3:49.8                                                         (1/20)       (1/167)                                           Water used for dilution                                                                      WHO standard WHO standard                                                     342 ppm      342 ppm                                           Con. of active in the                                                                        1.11%        0.13%                                             diluted sample                                                                Bloom at 0 time                                                                              spontaneous  spontaneous                                       After 20 inversions                                                                          excellent    excellent                                         Separation or Precipita-                                                      tion after mixing and                                                         standing for:                                                                  1 hour        none         none                                               2 hours       none         none                                               4 hours       none         none                                              10 hours       none         none                                              24 hours       none         none                                              ______________________________________                                    

EXAMPLE 3

A third series of experiments were carried out using the followingcompositions:

                  TABLE 3-1                                                       ______________________________________                                                            3.I   3.II                                                ______________________________________                                        1.     CGA (98% Tech)     20.4%   10.3%                                       2.     N-methylpyrrolidone                                                                              34.2%   38.5%                                       3.     N-octylpyrrolidone 17.0%   19.2%                                       4.     Soybean oil        17.0%   19.2%                                              (White Rose polyunsaturated                                                   vegetable oil)                                                         5.     Gafac E-610 (GAF)  11.4%   12.8%                                                                 100.0%  100.0%                                      ______________________________________                                    

The compositions were prepared by weighing out individual ingredients 1through 4 and dissolving the anionic emulsifier (5) in the admixture.The entire composition was mixed in an automatic rocking shaker toobtain a uniform and clear composition. Samples of the formulations Iand II were stored at -10° C. and 55° C. for each of three 24 hourperiods. No separation or precipitation of any ingredients was observedin the two samples. The concentrates thus obtained were each diluted ina standard 37 cm×2 cm Nessler's tube with two different diluents. In onecase, the diluent was deionized water and in the other case, acetic acidat pH 2.5. Two dilutions of emulsifiable concentrate to diluent at 1:20and 1:66 were prepared for each diluent. The bloom characteristics andemulsion stabilities of each of these dilutions are set forth in Table4.

                                      TABLE 3-2                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                         Formulation                                                                   I      II     III    IV     V      VI     VII    VIII                  __________________________________________________________________________    Emulsifiable                                                                         3.I    3.I    3.II   3.II   3.I    3.I    3.II   3.II                  concentrate                                                                   used                                                                          conc. of AAC                                                                         20.4%  20.4%  10.3%  10.3%  20.4%  20.4%  10.3%  10.3%                 water used                                                                           deionized                                                                            deionized                                                                            deionized                                                                            deionized                                                                            acetic acid at pH 2.5                      for dilution                                                                         water  water  water  water                                             dilution                                                                             2.5/50 0.3/50 2.5/50 0.3/50 2.5/50 0.3/50 2.5/50 10.3/50               factor                                                                        conc. in the                                                                         1.02%  0.12%  1.02%  0.12%  1.02%  0.12%  1.02%  0.12%                 diluted                                                                       sample                                                                        Bloom  spontaneous                                                                          spontaneous                                                                          spontaneous                                                                          spontaneous                                                                          spontaneous                                                                          spontaneous                                                                          spontaneous                                                                          spontaneous           before mixing                                                                        Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent             after 20                                                                             Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent                                                                            Excellent             inversions                                                                    separation                                                                    after mixing                                                                  and standing                                                                  for:                                                                          30 min.                                                                              *      *      *      *      yes, <1 mm                                                                           none   none   none                   1 hour                                                                              none   none   none   none   *      none   none   1 mm oil               2 hour                                                                              yes, 1-2 mm                                                                          none   none   none   *      none   none   *                      3 hour                                                                              *      *      *      *      *      1 mm   1 mm   *                      4 hour                                                                              yes    yes, 1-2 mm                                                                          none   none   *      *      *      *                      5 hour                                                                              yes    yes    yes    yes    *      *      *      *                     __________________________________________________________________________     *Not measured.                                                           

The above experiment was performed for evaluation of the formulation tobe used as a direct feed to host animals as an insecticide. Thecompositions 3.I and 3.II were also diluted with soybean oil to resultin 1000 ppm in AAC and did not form any ppt or separation. Thus, theformulation could be fed to the host animal (dogs) as is, or as adiluted sample in vegetable oil, e.g. soybean oil.

EXAMPLE 4

Use of N-octylpyrrolidone and N-dodecylpyrrolidone in combination.

A fourth series of experiments were carried out using the following fivecompositions:

                  TABLE 4-1                                                       ______________________________________                                                   4.1   4.2     4.3     4.4   4.5                                    ______________________________________                                        1. N-methylpyrroli-                                                                        33.0%   33.0%   33.0% 33.0% 33.0%                                   done                                                                       2. N-octylpyrrolidone                                                                      0%      10.0%   5.0%  7.5%  15.0%                                3. N-dodecylpyrroli-                                                                       15.? %  5.0%    1.0%  7.5%  0%                                      done                                                                       4. Aromatic petroleum                                                                      12.%    12.0%   12.%  12.0% 12.0%                                   oil - Exxon-200                                                            5. Gafac RE-610                                                                            14.2%   14.2%   14.2% 14.2% 14.2%                                   (GAF)                                                                      6. PRL (same as in                                                                         25.8%   25.8%   25.8% 25.8% 25.8%                                   Example 1):                                                                   92% Tech                                                                   ______________________________________                                                     100.0%  100.0%  100.0%                                                                              100.0%                                                                              100.0%                               ______________________________________                                    

The compositions were prepared as explained in Example 1. Each of theemulsified concentrates thus prepared was analyzed for ease ofemulsification and emulsion stability as explained under Example 1.Results are summarized in Table 4-2. These formulations passed threecycles of freeze-thaw between -10° C. and 55° C.

                                      TABLE 4-2                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                             Formulation                                                                   I    II   III  IV   V                                              __________________________________________________________________________    Emulsifiable                                                                             4.1  4.2  4.3  4.4  4.5                                            concentrate used                                                              conc. of AAC                                                                             25.8%                                                                              25.8%                                                                              25.8%                                                                              25.8%                                                                              25.8%                                          water used for                                                                           WHO 342 ppm hardness                                               dilution                                                                      dilution factor                                                                          1.2/48.8                                                                           1.2/48.8                                                                           1.2/48.8                                                                           1.2/48.8                                                                           1.2/48.8                                       conc. of CGA in                                                                          0.6% 0.6% 0.6% 0.6% 0.6%                                           diluted sample                                                                Bloom before mixing                                                                      Fair Excellent                                                                          Fair Excellent                                                                          Excellent                                      Bloom after                                                                              Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                      20 inversions                                                                 separation after mixing                                                       and standing for:                                                              1 hour    <1 mm                                                                              0    Trace                                                                              0    Trace                                           2 hour     1 mm                                                                              0    Trace                                                                              0    Trace                                           3 hour     1 mm                                                                              0    <1 mm                                                                              0    Trace                                          24 hour     2 mm                                                                              0     1 mm                                                                              0    Trace                                          __________________________________________________________________________

EXAMPLE 5 Tank Mix Compatibility

A formulation containing 16.6% of the ammonium salt of2-[4,5-dihydro-4-methyl-4-(1-methyl ethyl)-5 OXO-1 H-imidazol-2-yl]-3quinoline carboxylic acid, (referred to herein as SCP) in the water wasprepared by dissolving an appropriate quantity of the free acid in anammonium hydroxide solution containing a stoichiometric amount of thebase. The final pH was adjusted to 7.2. It is customary to use the PRLof Example 1 in conjunction with SCP in the ratio of 6:1 for better weedcontrol. The following experiment demonstrates the compatibility ofdifferent AAC's in the composition of the invention.

Formulations 4.1, 4.2, 4.3, 4.4, and 4.5 were diluted as shown inExample 4 and summarized in Table 4-2, except that 0.5 g of SCP (16.6%)was also added to the water. The effect on stability and emulsion bloomfrom the two AAC's present are summarized in Table 5-1.

                                      TABLE 5-1                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                  Mixed AAC's-Tank Mix Capability                                               Formulation                                                                              I    II   III  IV   V                                              __________________________________________________________________________    Emulsifiable                                                                             4.1  4.2  4.3  4.4  4.5                                            concentrate used                                                              (Example 4)                                                                   conc. of AAC                                                                             25.8%                                                                              25.8%                                                                              25.8%                                                                              25.8%                                                                              25.8%                                          (Example 1)                                                                   water used for                                                                           WHO 342 ppm hardness                                               dilution                                                                      conc. of PRL-SCP                                                                         1.05%                                                                              1.05%                                                                              1.05%                                                                              1.05%                                                                              1.05%                                          in diluted sample                                                             conc. of PRL                                                                             1.00%                                                                              1.00%                                                                              1.00%                                                                              1.00%                                                                              1.00%                                          in diluted sample                                                             conc. of SCP                                                                             0.5% 0.5% 0.5% 0.5% 0.5%                                           in diluted sample                                                             Bloom at 0-time                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                      before mixing                                                                 Bloom after                                                                              Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                      20 inversions                                                                 separation after mixing                                                       and standing for:                                                              1 hour    <2 mm                                                                              <2 mm                                                                              <1 mm                                                                              1 mm 2 mm                                            3 hour     2 mm                                                                               4 mm                                                                               1 mm                                                                              2 mm 4 mm                                           18 hour     2 mm                                                                               4 mm                                                                               2 mm                                                                              2 mm 4 mm                                           __________________________________________________________________________

Conclusion

Use of the two component system of the invention is advantages comparedto using either component alone in terms of ACC stability.

EXAMPLE 6

Tank mix compatibility was also demonstrated by making the followingformulations using PRL and a freezed-dried SCP. The followingformulation was prepared as explained in Example 1.

                                      TABLE 6-1                                   __________________________________________________________________________                  6.1  6.2  6.3  6.4  6.5                                         __________________________________________________________________________    1. N-methylpyrrolidone                                                                      35.3%                                                                              35.3%                                                                              35.3%                                                                              35.3%                                                                              35.3%                                       2. N-octylpyrrolidone                                                                       16.1%                                                                              12.0%                                                                              8.0% 4.0% 0%                                          3. N-dodecylpyrrolidone                                                                     0%   4.0% 8.0% 12.0%                                                                              16.0%                                       4. Aromatic petroleum                                                                       12.8%                                                                              12.8%                                                                              12.8%                                                                              12.8%                                                                              12.8%                                          oil-Exxon-200                                                              5. Gafac RE-610 (GAF)                                                                       9.2% 9.2% 9.2% 9.2% 9.2%                                        6. PRL: 92% Tech                                                                            23.0%                                                                              23.0%                                                                              23.0%                                                                              23.0%                                                                              23.0%                                       7. SCP        3.7% 3.7% 3.7% 3.7% 3.7%                                           (See Example 6A)                                                                         100.0%                                                                             100.0%                                                                             100.0%                                                                             100.0%                                                                             100.0%                                      __________________________________________________________________________

The formulations shown in Example 6, i.e., 6.1 through 6.5 were dilutedand the emulsion bloom and stability were evaluated as shown earlier.The results are summarized in Table 6-2. These formulations, i.e., 6.1through 6.5, passed three cycles of freeze-thaw at 5° C. to 55° C.

EXAMPLE 6A

16.8 g of SCP 97.4% Tech. were stirred with 52 ml in ammonium hydroxideuntil complete solution resulted. The sample was filtered over a Whatman#4 filter under suction. The filtrate was freeze-dried at 80° C. and≦1000 milliliter vacuum for a period of 24 hours.

                                      TABLE 6-2                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                  Formulation                                                                              I     II    III   IV    V                                          __________________________________________________________________________    Emulsifiable                                                                             6.1   6.2   6.3   6.4   6.5                                        concentrate used                                                              conc. of PRL                                                                             23.0% 23.0% 23.0% 23.0% 23.0%                                          SCP    3.7%  3.7%  3.7%  3.7%  3.7%                                       water used for                                                                           WHO 342 ppm hardness                                               dilution                                                                      dilution   2.5/47.5                                                                            2.5/47.5                                                                            2.5/47.5                                                                            2.5/47.5                                                                            2.5/47.5                                   factor                                                                        conc. of PRL                                                                             1.15% 1.15% 1.15% 1.15% 1.15%                                      in diluted sample                                                             conc. of SCP                                                                             0.185%                                                                              0.185%                                                                              0.185%                                                                              0.185%                                                                              0.185%                                     in diluted sample                                                             Bloom upon Good  Good  Good  Fair  Excellent                                  addition                                                                      Bloom after                                                                              Excellent                                                                           Excellent                                                                           Excellent                                                                           Excellent                                                                           Excellent                                  20 inversions                                                                 separation 4 mm  4 mm  4 mm  4 mm  2 mm                                       before mixing                                                                 separation after mixing                                                       and standing for:                                                              1 hour    4 mm  4 mm  2 mm  2 mm  2 mm                                        4 hour    4 mm  4 mm  2 mm  2 mm  3 mm                                       18 hour    4 mm  4 mm  2 mm  2 mm  3 mm                                       __________________________________________________________________________

Formulations 6.3 and 6.4 produced improved stability on dilution. Thecream re-emulsified after 10 inversions and reappeared 15 minutes afterthe 10 inversions.

EXAMPLE 7

The following formulations 7.1 through 7.5 were prepared exactly asexplained in Example 1, except that N³,N³,di-N-propyl-2,3-dinitro-6-trifluoromethyl-M-phenylenediamine (PRO) wasused. These formulations passed three cycles of freeze-thaw at 5° C. to55° C.

                                      TABLE 7-1                                   __________________________________________________________________________                  7.1  7.2  7.3  7.4  7.5                                         __________________________________________________________________________    1  N-methylpyrrolidone                                                                      34.7%                                                                              34.7%                                                                              34.7%                                                                              34.7%                                                                              34.7%                                       2. N-octylpyrrolidone                                                                       15.8%                                                                              11.8%                                                                              7.9% 4.0% 0%                                          3. N-dodecylpyrrolidone                                                                     0%   4.0% 7.9% 11.8%                                                                              15.8%                                       4. Aromatic petroleum                                                                       12.6%                                                                              12.6%                                                                              12.6%                                                                              12.6%                                                                              12.6%                                          oil-Exxon-200                                                              5. Gafac RE-610 (GAF)                                                                       10.6%                                                                              10.6%                                                                              10.6%                                                                              10.6%                                                                              10.6%                                       6. PRO: 94.7% Tech                                                                          26.3%                                                                              26.3%                                                                              26.3%                                                                              26.3%                                                                              26.3%                                                     100.0%                                                                             100.0%                                                                             100.0%                                                                             100.0%                                                                             100.0%                                      __________________________________________________________________________

The above formulations were diluted and the emulsion characteristicswere evaluated as before. The results are summarized in Table 8. Theresults show that the use of dodecylpyrrolidone or a mixture of 75:25N-dodecylpyrrolidone and N-octylpyrrolidone used as the second componentresulted in better emulsion stability when compared to use ofN-octylpyrrolidone alone.

                                      TABLE 7-2                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                  Formulation                                                                              I    II   III   IV   V                                             __________________________________________________________________________    Emulsifiable                                                                             7.1  7.2  7.3   7.4  7.5                                           concentrate used                                                              conc. of PRO                                                                             26.3%                                                                              26.3%                                                                              26.3% 26.3%                                                                              26.3%                                         water used for                                                                           WHO 342 ppm hardness                                               dilution                                                                      dilution factor                                                                          2.5/47.5                                                                           2.5/47.5                                                                           2.5/47.5                                                                            2.5/47.5                                                                           2.5/47.5                                      conc. of PRO in                                                                          1.31%                                                                              1.31%                                                                              1.31% 1.31%                                                                              1.31%                                         diluted sample                                                                Bloom at 0-time                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                           Excellent                                                                          Excellent                                     before mixing                                                                 Bloom after                                                                              Excellent                                                                          Excellent                                                                          Excellent                                                                           Excellent                                                                          Excellent                                     20 inversions                                                                 separation 1 mm 1 mm Trace 0    0                                             before mixing                                                                 separation after mixing                                                       and standing for:                                                             0 hour     2 mm 2 mm 0     0    0                                             1 hour     2 mm 2 mm <1 mm Trace                                                                              Trace                                         2 hour     3 mm 3 mm 1.5                                                                              mm 1 mm 1 mm                                          3 hour     3 mm 3 mm 1.5                                                                              mm 1 mm 1 mm                                          4 hour     4 mm 4 mm 2  mm 1 mm 1 mm                                          __________________________________________________________________________

EXAMPLE 8

The following formulations 8.1 through 8.16 were prepared exactly asexplained in Example 1 except that a fungicide N,N'-(1,4-piperazinediylbis (2,2,2-trichloro) ethylidene)bisformamide (TRI) was used.

                                      TABLE 8-1                                   __________________________________________________________________________                  8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9                             __________________________________________________________________________      N-methylpyrrolidone                                                                       42.6%                                                                             42.6%                                                                             42.6%                                                                             42.6%                                                                             42.6%                                                                             42.6%                                                                             42.6%                                                                             44.0%                                                                             15.0%                             N-octylpyrrolidone                                                                        19.4%                                                                             19.4%                                                                             9.7%                                                                              9.7%                                                                              --  --  --  10.0%                                                                             40.0%                             N-dodecylpyrrolidone                                                                      --  --  9.7%                                                                              9.7%                                                                              19.4%                                                                             19.4%                                                                             19.4%                                                                             10.0%                                                                             --                                Aromatic petroleum                                                                        15.5%                                                                             15.5%                                                                             15.5%                                                                             15.5%                                                                             15.5%                                                                             15.5%                                                                             15.5%                                                                             16.0%                                                                             --                                oil - Exxon-200                                                               Gafac RE-610                                                                              6.4%                                                                              --  6.4%                                                                              --  6.4%                                                                              --  --  10.0%                                                                             --                                Gafac RM-710                                                                              --  6.4%                                                                              --  6.4%                                                                              --  6.4%                                                                              --  --  5.0%                              TRI         16.1%                                                                             16.1%                                                                             16.1%                                                                             16.1%                                                                             16.1%                                                                             16.1%                                                                             16.1%                                                                             10.0%                                                                             7.5%                              Dodecyl benzene                                                                           --  --  --  --  --  --  6.4%                                                                              --  --                                sulfonic acid Tech: 97%                                                       Aromatic petroleum                                                                        --  --  --  --  --  --  --  --  32.5%                             oil - Texaco-150                                                            10.                                                                             Iso octylpyrrolidone                                                                      --  --  --  --  --  --  --  6.4%                                                                              --                                (N-2'ethyl hexyl-                                                             pyrrolidone)                                                                              100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                          __________________________________________________________________________                          8.10                                                                              8.11                                                                              8.12                                                                              8.13                                                                              8.14                                                                              8.15                                                                              8.16                            __________________________________________________________________________            1.                                                                              N-methylpyrrolidone                                                                       24.0%                                                                             24.0%                                                                             24.0%                                                                             32.0%                                                                             32.0%                                                                             32.0%                                                                             24.0%                                   2.                                                                              N-octylpyrrolidone                                                                        32.0%                                                                             16.0%                                                                             --  32.0%                                                                             16.0%                                                                             --  --                                      3.                                                                              N-dodecylpyrrolidone                                                                      --  16.0%                                                                             32.0%                                                                             --  16.0%                                                                             32.0%                                                                             --                                      4.                                                                              Aromatic petroleum                                                                        24.0%                                                                             24.0%                                                                             24.0%                                                                             16.0%                                                                             16.0%                                                                             16.0%                                                                             24.0%                                     oil - Exxon-200                                                             5.                                                                              Gafac RE-610                                                                              8.0%                                                                              8.0%                                                                              8.0%                                                                              8.0%                                                                              8.0%                                                                              8.0%                                                                              8.0%                                    6.                                                                              Gafac RM-710                                                                              --  --  --  --  --  --  --                                      7.                                                                              TRI         12.0%                                                                             12.0%                                                                             12.0%                                                                             12.0%                                                                             12.0%                                                                             12.0%                                                                             12.0%                                   8.                                                                              Dodecyl benzene                                                                           --  --  --   -- --  --  --                                        sulfonic acid Tech: 97%                                                     9.                                                                              Aromatic petroleum                                                                        --  --  --  --  --  --  --                                        oil - Texaco-150                                                            10.                                                                             Iso octylpyrrolidone                                                                      --  --  --  --  --  --  32.0%                                     (N-2'ethyl hexyl-                                                             pyrrolidone)                                                                              100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                                                                            100.0%                          __________________________________________________________________________

The ease of emulsification and emulsion stability of the above sixformulations were evaluated after dilution, as before, and the resultsare summarized in Table 8-2.

                                      TABLE 8-2                                   __________________________________________________________________________    EMULSION STABILITY AND BLOOM CHARACTERISTICS                                  __________________________________________________________________________                Formulation                                                                   I    II   III  IV   V    VI   VII  VIII IX                        __________________________________________________________________________    Emulsifiable                                                                              8.1  8.2  8.3  8.4  8.5  8.6  8.7  8.8  8.9                       concentrate used                                                              conc. of TRI                                                                              16.1%                                                                              16.1%                                                                              16.1%                                                                              16.1%                                                                              16.1%                                                                              16.1%                                                                              16.1%                                                                              10%  7.5%                      water used for dilution                                                                   WHO 342 ppm hardness                                              dilution factor                                                                           2.45/47.5                                                                          2.45/47.5                                                                          2.45/47.5                                                                          2.45/47.5                                                                          2.45/47.5                                                                          2.45/47.5                                                                          2.45/47.5                                                                          0.8/49.2                                                                           1.0/49                    conc. of TRI in                                                                           0.81%                                                                              0.81%                                                                              0.81%                                                                              0.81%                                                                              0.81%                                                                              0.81%                                                                              0.81%                                                                              0.16%                                                                              0.15%                     the diluted sample                                                            Bloom before mixing                                                                       Fair-                                                                              Fair Fair-                                                                              Fair Fair-                                                                              Fair-                                                                              Poor Poor Poor                                  Good      Good      Good Good                                     after 20 inversions                                                                       Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                 separation at 0 time                                                                      4 mm 5 mm 3 mm 5 mm 3.5 mm                                                                             --   8 mm                                ppt/separations after                                                         mixing and standing for:                                                       0 hour     0    0    0    0    0    0    0                                    1 hour     2 mm 2 mm   2 mm                                                                             4 mm   2 mm                                                                               2 mm                                                                             4 mm, oil                                                                          --   --                         2 hour     2 mm 2 mm   2 mm                                                                             4 mm   2 mm                                                                               3 mm                                                                             4 mm, oil                                                                          Trace                                                                              0                          4 hour     4 mm 4 mm 3.5 mm                                                                             5 mm 3.5 mm                                                                             3.5 mm    <1 mm                                                                              0                         24 hour                                         1 mm                                                                              1 mm                                                                          oil on top                *after 24 hour settling,                                                      filtered through screens                                                       60 mesh                                       +    -                         100 mesh                                       +    -                         250 mesh                                       ++   -                         __________________________________________________________________________                          Formulation                                                                   X    XI   XII  XIII XIV  XV   XVI                       __________________________________________________________________________              Emulsifiable                                                                              8.10 8.11 8.12 8.13 8.14 8.15 8.16                                concentrate used                                                              conc. of TRI                                                                              12%  12%  12%  12%  12%   12% 12%                                 water used for dilution                                                                   WHO 342 ppm hardness                                              dilution factor                                                                           0.7/49.3                                                                           0.7/49.3                                                                           0.7/49.3                                                                           0.7/49.3                                                                           0.7/49.3                                                                           0.7/49.3                                                                           0.7/49.3                            conc. of TRI in                                                                           0.17%                                                                              0.17%                                                                              0.17%                                                                              0.17%                                                                              0.17%                                                                              0.17%                                                                              0.17%                               the diluted sample                                                            Bloom before mixing                                                                       Fair Good Fair Fair Fair Fair Fair                                after 20 inversions                                                                       Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                           separation at 0 time                                                          ppt/separations after                                                         mixing and standing for:                                                       0 hour                                                                        1 hour     Trace                                                                              Trace                                                                              0    Trace                                                                              Trace                                                                              Trace                                                                              Trace                                2 hour     --   --   --   --   --   --   --                                   4 hour     Trace                                                                              Trace                                                                              Trace                                                                              <1 mm                                                                              <1 mm                                                                              Trace                                                                              <1 mm                               24 hour     1.5 mm                                                                             1 mm <1 mm                                                                               1.5 mm                                                                             1 mm                                                                              1 mm <1 mm                               *after 24 hour settling,                                                      filtered through screens                                                       60 mesh    -    ++   ++   +    -    -    +                                   100 mesh    +    +    +    +    +    -    +                                   250 mesh    +    ++   ++   ++   ++   +    ++                        __________________________________________________________________________     * - means no sediment; + means trace; ++ means more than trace sediment       but unmeasurable by weighing.                                            

EXAMPLE 9

The following formulation 9.1 was prepared exactly as explained inExample 1, except that N-(2'-ethylhexylpyrrolidone) was used in theplace of N-octylpyrrolidone.

                  TABLE 9-1                                                       ______________________________________                                        Formulation and % Composition                                                                         9.1                                                   ______________________________________                                        1.       N-methylpyrrolidone  33.0%                                           2.       N-(2'-ethylhexylpyrrolidone)                                                                       15.0%                                           3.       Aromatic Petroleum                                                            oil - Exxon 200      12.0%                                           4.       PRL Tech. 92% (see                                                            Example 1)           26.0%                                           5.       Gafac RE-610 (GAF)   14.0%                                                    TOTAL                100.0%                                          ______________________________________                                    

This formulation did not freeze at 5° C. The ease of emulsification andstability on dilution are shown in Table 9-2.

                  TABLE 9-2                                                       ______________________________________                                                        Formulation                                                                   9.1                                                           ______________________________________                                        Conc. of PRL:     26.0%                                                       Water used for dilution                                                                         WHO 342 PPM hardness                                        Dilution factor   2.5 g/47.5 g                                                Conc. of PRL in the                                                                             1.3%                                                        diluted sample                                                                Bloom at 0 time   Excellent                                                   Bloom after 20    Excellent                                                   inversions                                                                    Separation of cream                                                           after 20 inversions                                                           and on standing after:                                                         1 hour           Trace                                                        3 hours          <1 mm                                                        4 hours          <1 mm                                                       24 hours          <1 mm                                                       ______________________________________                                    

After standing for 24 hours, 20 inversions and filtration through 60mesh, 100 mesh and 250 mesh screens, no sediment was left, even on a 250mesh screen.

What is claimed is;
 1. A stable emulsifiable concentrate comprising anagricultural active chemical which is substantially insoluble in water,an organic diluent, a surfactant and a solvent composed of first andsecond components, said first component having a sufficiently highhydrophilic property and being present in an amount effective tosolubilize the agriculturally active chemical and is selected from thegroup consisting of pyrrolidones having the formula ##STR4## wherein Ris hydrogen or lower alkyl and R₁ is lower alkyl, wherein lower alkyl isan alkyl group having from 1 to 4 carbon atoms, and the second componenthaving an HLB value of from about 2 to 8 and being present in an amount,in conjunction with a surfactant, effective to disperse theagriculturally active chemical and is selected from the group consistingof pyrrolidones having a formula ##STR5## wherein R₂ is hydrogen oralkyl having from 6 to 14 carbon atoms and R₃ is alkyl having from 6 to14 carbon atoms with the proviso that at least one of R₂ or R₃ must becontain at least 6 carbon atoms and the sum of the carbon atoms in R₂and R₃ cannot exceed 14;and combinations thereof, wherein the alkylportion may be distributed at one or more sites on the ring so long asone portion contains at least 6 carbon atoms and the total number ofalkyl carbon atoms does not exceed
 14. 2. The concentrate of claim 1wherein the first component is selected from the group consisting ofN-methylpyrrolidone, ethylene carbonate, propylene carbonate, butylenecarbonate, N-N,dimethylimidazolone, dimethylformamide, dimethylacetamideand dimethylsulfoxide, and mixtures thereof.
 3. The concentrate of claim1 wherein the first component is N-methylpyrrolidone.
 4. The concentrateof claim 1 wherein the organic diluent is an oil having a fractionaldispersive solubility parameter of a greater than about 70% and a molarvolume of greater than about 90 cm³ /mole.
 5. The concentrate of claim 4wherein the diluent is selected from the group consisting of soybeanoil, rape seed oil, long chain alcohols, long chain ketones, long chainesters, and ethers, and aromatic petroleum oils.
 6. The concentrate ofclaim 5 wherein the diluent is an aromatic petroleum oil comprisingabout 60% of heavy aromatic solvent naphtha and about 40% of middledistillate solvent extractant.
 7. The concentrate of claim 1 wherein thesecond component is selected from the group consisting ofoctyl-pyrrolidone, dodecylpyrrolidone, N-2-ethylhexylpyrrolidone, andmixtures thereof.
 8. The concentrate of claim 1 wherein theagriculturally active chemical is selected from the group consisting offertilizers, plant nutrients, plant growth accelerants, plant growthcontrolling agents, insecticides, bactericides, fungicides, nematocides,defoliants, and fumigants.
 9. The concentrate of claim 8 wherein theagriculturally active chemical is an insecticide selected from the groupconsisting of cyclo compounds, carbamates, animal and plant derivatives,synthetic pyrethoids, diphenyl compounds, nonphosphates, organicphosphates, thiophosphates, and dithiophosphates.
 10. The concentrate ofclaim 1 wherein the agriculturally active chemical is a herbicideselected from the group consisting of phenoxy compounds, benzoic acid,acetic acid, phthalic acid, aniline derivatives, nitriles, amides,acetamides, anilides, carbamates, thiocarbamates, heterocyclic nitrogenderivatives, urea derivatives, and phosphates.
 11. The concentrate ofclaim 1 wherein the agriculturally active compound is a fungicideselected from the group consisting of organic compounds and morpholines.12. The concentrate of claim 1 wherein the agriculturally activecompound is a fumigant, growth regulator, repellent or rodenticide. 13.The concentrate of claim 1 wherein the agriculturally active compound isa pesticide.
 14. The concentrate of claim 1 the amount of solvent is inthe range from about 20 to 90%, and the amount of diluent is in therange from about 80 to 10%, each amount being based on the total weightof solvent and diluent in the concentrate.
 15. The concentrate of claim14 wherein the amount of the first component is from about 5 to 95% andthe amount of the second component is from about 5 to 95% based on theweight of the solvent in the concentrate.
 16. The concentrate of claim15 wherein the amount of surfactant is from about 1 to 25% by weightbased on the total weight of the concentrate.
 17. The concentrate ofclaim 16 wherein the concentration of the agriculturally active chemicalis in excess of about 5 weight percent, based on the weight of the totalconcentrate.
 18. The concentrate of claim 17 wherein the amount of theagriculturally active chemical is from about 5% to 60% by weight basedon the total weight of the concentrate.
 19. A composition comprising theemulsifiable concentrate of claim 1 and water wherein the agriculturallyactive chemical is present in an effective agriculturally active amount.20. A method for treatment of plants comprising applying to said plantor the soil surrounding said plant the composition of claim
 19. 21. Amethod of treatment of pests on animals comprising applying to saidanimal the composition of claim
 19. 22. A method of controlling thepopulation of agricultural pests by applying to the pests thecomposition of claim
 19. 23. The method of claim 22 wherein the pestsare microorganisms.